EP0681522B1 - Grossporiger schaumstoff und sein herstellungsverfahren - Google Patents

Grossporiger schaumstoff und sein herstellungsverfahren Download PDF

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Publication number
EP0681522B1
EP0681522B1 EP94903474A EP94903474A EP0681522B1 EP 0681522 B1 EP0681522 B1 EP 0681522B1 EP 94903474 A EP94903474 A EP 94903474A EP 94903474 A EP94903474 A EP 94903474A EP 0681522 B1 EP0681522 B1 EP 0681522B1
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EP
European Patent Office
Prior art keywords
foam structure
cell size
agent
polymer material
alkenyl aromatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94903474A
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English (en)
French (fr)
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EP0681522A1 (de
EP0681522A4 (de
Inventor
Kyung W. Suh
Masayuki Wakabayashi
Chau V. Vo
Andrew N. Paquet
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Dow Chemical Co
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Dow Chemical Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/13—Cell size and distribution control while molding a foam

Definitions

  • This invention relates to a process for making a closed-cell, alkenyl aromatic polymer foam structure having an enlarged average cell size.
  • pristine blowing agents typically include inorganic blowing agents such as carbon dioxide, nitrogen, water, and argon.
  • a problem with using pristine blowing agents is maintaining desirable morphology in the resulting foam structure.
  • One characteristic of the morphology is cell size.
  • a desirable cell size can be difficult to maintain when using pristine (inorganic) blowing agents, particularly carbon dioxide, because of their relatively high nucleation and expansion rates.
  • Prior art attempts to make a foam structure having an enlarged cell size include the integration of a wax in a foam-forming gel prior to extrusion of the gel through a die to form the foam structure.
  • a wax is seen in U.S. Patent No. 4,229,396.
  • Use of a wax may, however, create processing problems and physical property abherations in the foam structure.
  • the wax may cause thermal stability variations or diminution in physical properties in the foam structure.
  • the wax may also cause inconsistency in extrusion temperatures.
  • foam structure with a blowing agent comprised partially or entirely of a pristine blowing agent with a desirable (enlarged) average cell size. It would further be desirable to make such foam structures with non-pristine blowing agents. It would further be desirable to make such foam structures while retaining desirable physical properties and thermal stability. It would be further desirable to make such foam structures without using a wax.
  • a process for making a closed-cell, alkenyl aromatic polymer foam structure having an enlarged average cell size comprises: a) heating an alkenyl aromatic polymer material to form a melt polymer material; b) incorporating a substantially non-waxy cell size enlarging agent into the melt polymer; c) incorporating a blowing agent into the melt polymer material at an elevated pressure to form a foamable gel; and d) expanding the foamable gel at a reduced pressure to form a foam structure.
  • the alkenyl aromatic polymer comprises greater than 50 percent by weight alkenyl aromatic monomeric units.
  • the enlarging agent is incorporated in an amount sufficient to enlarge the average cell size of the foam structure by about 20 percent or more over a corresponding foam structure made without the enlarging agent. Further, the enlarging agent is incorporated in a quantity such that the foam structure has physical properties similar to those of the corresponding foam structure without the cell size enlarging agent.
  • the present foam structure comprises an alkenyl aromatic polymer material.
  • Suitable alkenyl aromatic polymer materials include alkenyl aromatic homopolymers and copolymers of alkenyl aromatic compounds and copolymerizable ethylenically unsaturated comonomers.
  • the alkenyl aromatic polymer material may further include minor proportions of non-alkenyl aromatic polymers.
  • the alkenyl aromatic polymer material may be comprised solely of one or more alkenyl aromatic homopolymers, one or more alkenyl aromatic copolymers, a blend of one or more of each of alkenyl aromatic homopolymers and copolymers, or blends of any of the foregoing with a non-alkenyl aromatic polymer.
  • the alkenyl aromatic polymer material comprises greater than 50 and preferably greater than 70 weight percent alkenyl aromatic monomeric units. Most preferably, the alkenyl aromatic polymer material is comprised entirely of alkenyl aromatic monomeric units.
  • Suitable alkenyl aromatic polymers include those derived from alkenyl aromatic compounds such as styrene, alphamethylstyrene, ethylstyrene, vinyl toluene, chlorostyrene, and bromostyrene.
  • a preferred alkenyl aromatic polymer is polystyrene.
  • Minor amounts of monoethylenically unsaturated compounds such as C 2-4 alkyl acids and esters, ionomeric derivatives, and C 4-6 dienes may be copolymerized with alkenyl aromatic compounds.
  • copolymerizable compounds include acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylonitrile, maleic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate and butadiene.
  • Preferred structures comprise substantially (that is, greater than 95 percent) and most preferably entirely of polystyrene because polystyrene foam is economical, and is commonly employed as an insulating plastic foam.
  • the present alkenyl aromatic polymer foam is generally prepared by heating an alkenyl aromatic polymer material to form a plasticized or melt polymer material, incorporating therein a blowing agent to form a foamable gel, and extruding the gel through a die to form the foam product.
  • a blowing agent Prior to mixing with the blowing agent, the polymer material is heated to a temperature at or above its glass transition temperature or melting point.
  • the blowing agent may be incorporated or mixed into the melt polymer material by any means known in the art such as with an extruder, mixer, or blender.
  • the blowing agent is mixed with the melt polymer material at an elevated pressure sufficient to prevent substantial expansion of the melt polymer material and to generally disperse the blowing agent homogeneously therein.
  • a nucleator may be blended in the polymer melt or dry blended with the polymer material prior to plasticizing or melting.
  • the foamable gel is typically cooled to a lower temperature to optimize physical characteristics of the foam structure.
  • the gel is then extruded through a die of desired shape to a zone of lower or reduced pressure to form the foam structure.
  • the zone of lower pressure is at a pressure lower than that in which the foamable gel is maintained prior to extrusion through the die.
  • the lower pressure may be superatmospheric or subatmospheric (vacuum), but is preferably at an atmospheric level.
  • Blowing agents useful in making the present foam structure include inorganic agents, organic blowing agents and chemical blowing agents.
  • Suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, and helium.
  • a useful blowing agent is a blend of carbon dioxide and water.
  • Organic blowing agents include aliphatic hydrocarbons having 1-9 carbon atoms and fully and partially halogenated aliphatic hydrocarbons having 1-4 carbon atoms. Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, and neopentane.
  • Fully and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons, and chlorofluorocarbons.
  • fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, difluoromethane, 1-1-difluoroethane, 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane, perfluoroethane, 1,1,1-trifluoropropane, perfluoropropane, difluoropropane such as 2,2-difluoropropane, perfluorobutane, perfluorocyclobutane.
  • Partially halogenated chlorocarbons and chlorofluorocarbons for use in this invention include dichloropropane, methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, chlorodifluoromethane (HCFC-22), 1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124).
  • Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, and dichlorohexafluoropropane.
  • a useful blowing agent is a blend of HCFC-142b and carbon dioxide and optionally HCFC-22.
  • Chemical blowing agents include azodicarbonamide, azobis(isobutyronitrile), benzenesulfonhydrazide, 4-hydroxybenzene sulfonyl-semicarbazide, p-toluene sulfonyl semi-carbazide, barium azodicarboxylate, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, and trihydrazino triazine.
  • inorganic blowing agents For environmental reason, it is desirable to employ inorganic blowing agents whenever possible.
  • Two particularly desirable inorganic blowing agents are carbon dioxide and water.
  • the amount of blowing agent incorporated into the polymer melt material to make a foam-forming polymer gel is from 0.2 to 5.0, preferably from 0.5 to 3.0, and most preferably from 1.0 to 2.50 moles per kilogram of polymer.
  • the foam component of the present foam structure has a density of from 10 to 150 and most preferably from 10 to 70 kilograms per cubic meter (kg/m 3 ).
  • the foam structure has an average cell size of from 0.1 to 5.0 millimeters and preferably from 0.15 to 2.4 millimeters according to ASTM D3576.
  • the cell size enlarging agent has the capability to and is present in an amount sufficient to enlarge or increase the average cell size of the present foam structure over that of a corresponding foam structure without the agent.
  • the average cell size is enlarged or increased by 20 percent or more and preferably by 30 percent or more over that of the corresponding foam without the agent.
  • the average cell size refers to the cell size of the present foam structure 30 minutes after extrusion or expansion thereof according to ASTM D3576.
  • the cell size enlarging agent is preferably present at from 0.05 to 5.0 parts per hundred and more preferably from 0.1 to 3 parts per hundred based upon the weight of the alkenyl aromatic polymer material.
  • the cell size enlarging agent is an organic material which melts below the foaming temperature of the alkenyl aromatic polymer foam structure. Foaming temperatures for alkenyl aromatic polymer foam structures typically range from 110°C to 135°C. The cell size enlarging agent either partly or substantially dissolves in the foamable gel of the polymer and blowing agent at the foaming temperature.
  • the cell size enlarging agent is of a nature and is present in an amount such that it does not deleteriously impact the physical properties of the present foam structure.
  • the present foam structure has physical properties substantially similar or the same in the degree as a corresponding foam structure without the cell size enlarging agent. These physical properties include compressive strength (according to ASTM D1621-79), heat distortion temperature (according to ASTM D2126-87) and environmental dimensional change (according to ASTM D2126-87). Physical properties, specifically those described above, preferably are within 10 percent (10 percent or less) of that of the corresponding foam structure without the cell size enlarging agent.
  • the present foam structure is preferably more dimensionally stable than the corresponding foam structure without the cell size enlarging agent.
  • the cell size enlarging agent is also substantially non-waxy.
  • the agent is substantially non-waxy in that it usually takes a liquid form at both ambient and elevated temperatures, such as at typical foaming temperatures of 110°C-135°C.
  • the agent may, however, take a solid form at ambient temperature if it is substantially resistant to deformation at that temperature.
  • a waxy substance is typically a solid deformable at ambient temperature without the application of heat or elevated temperature.
  • Suitable non-waxy cell size enlarging agents are diverse in chemical structure, and include the following: polyethylene glycol and polypropylene glycol of 1200 or more molecular weight, salts of N-tallow beta amino dipropionate, amine oxides, imidazoline, fatty acid alkanolamides of C 12-18 , n-alkyl trimethyl ammonium chloride, ethoxylated linear alcohols, dioctyl ester of sodium sulfosuccinic acid, polyoxy-ethylene sorbitan monopalmitate, diglycol laurate, fluorochemical surfactants, coco betaine, aqueous emulsions and fluids of silicone compounds such as dimethyl polysiloxane.
  • the cell size enlarging agent of the present invention is further distinguished from the prior art plasticizing agents because it affects the desired enlargement of average cell size without deleteriously affecting the physical properties of the foam structure.
  • Prior art plasticizers such as those seen in Great Britain Patent No. 1,316,465, U.S. Patent No. 4,940,735, and Japanese Patent No. 47-25147 may enlarge or increase cell size, but also may deleteriously or negatively impact physical properties, including those described above.
  • low molecular weight ( ⁇ 1000 weight average molecular weight) organic and inorganic compounds and polymers may enlarge cell size, but also may cause diminution in desirable physical properties.
  • higher weight average molecular weight compounds and polymers may not cause diminution in physical properties, but may not enlarge cell size.
  • certain organic and inorganic compounds and polymers were discovered to cause cell size enlargement without diminution in physical properties.
  • the foam component of the present foam structure is closed cell.
  • the present foam is greater than 90 percent closed-cell according to ASTM D2856-A.
  • additives may be incorporated in the present foam structure such as inorganic fillers, pigments, antioxidants, acid scavengers, ultraviolet absorbers, flame retardants, processing aids, and extrusion aids.
  • nucleating agent may be added in order to control the size of foam cells.
  • Preferred nucleating agents include inorganic substances such as calcium carbonate, talc, clay, titanium oxide, silica, barium sulfate, diatomaceous earth, and mixtures of citric acid and sodium bicarbonate.
  • the amount of nucleating agent employed may range from 0.01 to 5 parts by weight per hundred parts by weight of a polymer resin. The preferred range is from 0.1 to 3 parts by weight.
  • the present foam structure may be used to insulate a surface by applying to the surface an insulating panel fashioned from the present structure.
  • Such panels are useful in any conventional insulating applications such as roofing, buildings, and refrigerators.
  • the present foam structure may be formed into a plurality of discrete foamed particles for conventional loose-fill cushioning and packaging applications, or may be ground into scrap for use as blown insulation.
  • Foam structures were made in accordance with the present invention, and tested for cell size and retention of certain desirable physical properties.
  • the physical properties include density, compressive strength, heat distortion temperature, and environmental dimensional change.
  • the foam structures were made with an apparatus comprising an extruder, a mixer, a cooler, and a die in sequence. Polymer feedstock and additives other than the blowing agent were dry blended and fed to the extruder. The blowing agent was injected into the polymer melt in the mixer to form a foamable gel. The foamable gel was cooled in the cooler, and conveyed through a die into a region of lower pressure to form the foam structure.
  • the polymer feedstock employed was a granular polystyrene having a weight average molecular weight of 200,000 according to size exclusion chromatography.
  • Density was measured according to ASTM D1622. Two specimens of each sample were averaged. Foam structure skins were removed for the tests.
  • Compressive strength was measured according to ASTM D1621-79. Two specimens of each sample were averaged. Foam structure skins were removed.
  • the heat distortion temperature (HDT) was measured according to ASTM D2126-87. Two specimens of each sample were averaged. Foam structure skins were removed. Each specimen was kept at 165°F/ambient humidity for three days and the temperature was increased in increments of 5°F until specimens failed.
  • EDC Environmental dimensional changes
  • the extruder used was a 1-1/4 inch (in) (3.1 centimeters (cm)) screw type extrusion line with a slit die.
  • the foamable gel was cooled to a uniform foaming temperature of 125°C-130°C. Blowing agent content, process conditions, and physical property values of the resulting foam structures are represented in Table 1.
  • the foam structure of Run B exhibited a significantly higher cell size versus the foam structure of control Run A. Further, the skin quality was better.
  • the foam structures of Runs D and E also exhibited significantly greater cell size than the foam structure of control Run C.
  • the foam structures of Runs D and E exhibited better skin quality as well.
  • the extruder used was a 2-1/2 in (6.3 cm) screw type extrusion line with a 1 in (2.5 cm) wide slit die.
  • 1.0 pph hexabromocyclododecane (HBCD) was dry-blended with the polymer.
  • the foam structure was expanded between substantially parallel forming plates downstream of the die. Blowing agent content, process conditions, and physical property values of the foam structures are represented in Tables 2A and 2B.
  • Foam structures were produced using the apparatus and formulation of Example 2 except for a change in blowing agent and enlarging agent content. Blowing agent content, process conditions, and physical property values for the foam structures are represented in Tables 3A and 3B.
  • Foam structures were produced using the same formulation and apparatus of Example 3 except that a 3 in (7.5 cm) wide slit die and different enlarging agents were used. Blowing agent content, process conditions, and physical property values for the foam structures are represented in Tables 4A and 4B.
  • the extruder used was a 2 in (5.0 cm) screw type extrusion line with a slit die.
  • Additives included 0.15 pph barium stearate and 0.03 pph cyano-phthalo blue by weight based upon the weight of the polymer.
  • the foam structure was expanded between substantially parallel forming plates. Blowing agent content, process conditions, and physical property values for the foam structures are represented in Tables 5A and 5B.
  • Run R exhibited significantly higher cell size than the foam structure of control Run Q.
  • a plurality of materials were evaluated for cell-size enlarging capability.
  • One hundred parts by weight of polystyrene was introduced into a glass ampule along with 45 parts by weight of a one-to-one by weight mixture of methyl chloride and dichloro-difluoro methane.
  • the ampule was then cooled to dry ice temperature, sealed and permitted to warm to ambient temperature.
  • the ampule was then heated to a temperature of 200°C in an oil bath for a period of two to three hours until the polymer melted and a homogeneous mixture was obtained in the ampule.
  • the ampule was then cooled to the foaming temperature of 125°C for a period of about five to ten minutes.
  • the glass ampule was then ruptured to permit foaming polymer to extrude therefrom.
  • the cell-size enlarging agent was present in a proportion of one-half part by weight per one-hundred parts by weight polymer. The results are set forth in Table 6.
  • H.D.T. Heat Distortion Temperature after 210 days
  • E.D.C. Environmental Dimensional Change after 210 days

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Claims (9)

  1. Verfahren zur Herstellung einer geschlossenzelligen Schaumstruktur aus alkenylaromatischem Polymerem, welche eine vergrößerte Durchschnittszellgröße besitzt, umfassend:
    a) Erhitzen eines alkenylaromatischen Polymermaterials, das mehr als 50 Gew.-% alkenylaromatische Monomereneinheiten besitzt, zur Bildung eines geschmolzenen Polymermaterials;
    b) Eingeben eines Blähmittels in das geschmolzene Polymermaterial bei einem erhöhten Druck zur Bildung eines schäumbaren Gels; und
    c) Extrudieren des schäumbaren Gels durch eine Düse in einen Bereich von reduziertem Druck zur Bildung der Schaumstruktur;
    worin ein im wesentlichen nicht-wachsartiges Zellgrößenvergrößerungsmittel in das geschmolzene Polymermaterial in einer ausreichenden Menge eingegeben wird, um die Durchschnittszellgröße der Schaumstruktur um 20 % oder mehr gegenüber einer entsprechenden, ohne das Vergrößerungsmittel hergestellten Schaumstruktur zu vergrößern, und worin das Vergrößerungsmittel in einer solchen Menge eingegeben wird, daß die Schaumstruktur physikalische Eigenschaften vergleichbar denjenigen der entsprechenden Schaumstruktur ohne das Zellgrößenvergrößerungsmittel hat.
  2. Verfahren nach Anspruch 1, worin das schäumbare Gel auf eine optimale Schäumungstemperatur abgekühlt und durch Extrusion durch eine Düse zu einer Zone mit niedrigerem Druck expandiert wird.
  3. Verfahren nach Anspruch 2, worin ein Keimbildungsmittel in das geschmolzene Polymermaterial eingeben wird.
  4. Verfahren nach einem der Ansprüche 1 - 3, worin das Zellgrößenvergrößerungsmittel in einer Menge zur Vergrößerung der Durchschnittszellgröße der Schaumstruktur um 30 % oder mehr gegenüber der Zellgröße der entsprechenden, ohne ein Zellgrößenvergrößerungsmittel hergestellten Schaumstruktur eingegeben wird.
  5. Verfahren nach einem der Ansprüche 1 - 3, worin das Zellgrößenvergrößerungsmittel mit 0,05 bis 5 Teilen pro 100, bezogen auf das Gewicht das alkenylaromatischen Polymermaterials, eingegeben wird.
  6. Verfahren nach einem der Ansprüche 1 - 5, worin die physikalischen Eigenschaften aus Kompressionsfestigkeit, Hitzeverformungstemperatur und Umgebungs-Dimensionveränderung bestehen.
  7. Verfahren nach Anspruch 6, worin die physikalischen Eigenschaften innerhalb von 10 % derjenigen der entsprechenden, ohne ein Zellgrößenvergrößerungsmittel hergestellten Schaumstruktur liegen.
  8. Verfahren nach einem der Ansprüche 1 - 5, worin das Blähmittel Kohlendioxid enthält.
  9. Geschlossenzellige Schaumstruktur aus alkenylaromatischem Polymerem, erhältlich aus dem Verfahren eines der Ansprüche 1 - 8.
EP94903474A 1993-01-26 1993-12-07 Grossporiger schaumstoff und sein herstellungsverfahren Expired - Lifetime EP0681522B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US915593A 1993-01-26 1993-01-26
US9155 1993-01-26
PCT/US1993/011813 WO1994016876A1 (en) 1993-01-26 1993-12-07 Enlarged cell foam and method of making same

Publications (3)

Publication Number Publication Date
EP0681522A1 EP0681522A1 (de) 1995-11-15
EP0681522A4 EP0681522A4 (de) 1996-02-28
EP0681522B1 true EP0681522B1 (de) 1999-05-26

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EP94903474A Expired - Lifetime EP0681522B1 (de) 1993-01-26 1993-12-07 Grossporiger schaumstoff und sein herstellungsverfahren

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US (1) US5489407A (de)
EP (1) EP0681522B1 (de)
JP (1) JP3338450B2 (de)
KR (1) KR100312358B1 (de)
CA (1) CA2153321C (de)
DE (1) DE69325109T2 (de)
ES (1) ES2134339T3 (de)
FI (1) FI953558A (de)
GR (1) GR3030944T3 (de)
HU (1) HU216025B (de)
MX (1) MX9400652A (de)
TW (1) TW301662B (de)
WO (1) WO1994016876A1 (de)

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EP1930368A1 (de) 2006-12-08 2008-06-11 Basf Se Polystyrolextrusionsschaumstoff mit vergrösserten Zellen

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TW301662B (de) 1997-04-01
JPH08505895A (ja) 1996-06-25
GR3030944T3 (en) 1999-11-30
MX9400652A (es) 1994-08-31
FI953558A0 (fi) 1995-07-25
HU9502231D0 (en) 1995-09-28
CA2153321A1 (en) 1994-08-04
US5489407A (en) 1996-02-06
CA2153321C (en) 2002-05-07
HUT73153A (en) 1996-06-28
EP0681522A1 (de) 1995-11-15
KR100312358B1 (ko) 2002-11-01
KR960700143A (ko) 1996-01-19
FI953558A (fi) 1995-07-25
WO1994016876A1 (en) 1994-08-04
HU216025B (hu) 1999-04-28
DE69325109D1 (de) 1999-07-01
JP3338450B2 (ja) 2002-10-28
EP0681522A4 (de) 1996-02-28
DE69325109T2 (de) 1999-09-23

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